US3927146A - Compositions comprising mixtures of hydrogenphosphonates and methylphosphonates - Google Patents

Compositions comprising mixtures of hydrogenphosphonates and methylphosphonates Download PDF

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Publication number
US3927146A
US3927146A US535749A US53574974A US3927146A US 3927146 A US3927146 A US 3927146A US 535749 A US535749 A US 535749A US 53574974 A US53574974 A US 53574974A US 3927146 A US3927146 A US 3927146A
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United States
Prior art keywords
phosphite
compositions
methanol
mixtures
hydrogenphosphonates
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US535749A
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English (en)
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Wadim Batorewicz
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Uniroyal Chemical Co Inc
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Uniroyal Inc
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Priority to US535749A priority Critical patent/US3927146A/en
Priority to GB3001/75A priority patent/GB1503561A/en
Priority to IT67287/75A priority patent/IT1032571B/it
Priority to DE19752504828 priority patent/DE2504828A1/de
Priority to FR7503597A priority patent/FR2260600B1/fr
Priority to JP50015838A priority patent/JPS50108224A/ja
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Assigned to UNIROYAL CHEMICAL COMPANY, INC., WORLD HEADQUARTERS, MIDDLEBURY, CT. 06749, A CORP. OF NEW JERSEY reassignment UNIROYAL CHEMICAL COMPANY, INC., WORLD HEADQUARTERS, MIDDLEBURY, CT. 06749, A CORP. OF NEW JERSEY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UNIROYAL, INC., A NEW YORK CORP.
Assigned to UNIROYAL CHEMICAL COMPANY, INC. reassignment UNIROYAL CHEMICAL COMPANY, INC. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UNIROYAL, INC., A NJ CORP.
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • compositions of this invention are mixtures of hydrogenphosphonates and methylphosphonates. These compositions are obtained by reacting cyclic tertiary phosphites with methanol in the presence of a suitable acid catalyst.
  • the preferred mixtures of phosphonates are obtained by the process of this invention from trialkyl phosphites having bicyclic and spirocyclic structures.
  • the most preferred compositions are those derived from spirocyclic phosphites.
  • the acid catalysts which can be employed in the invention are sulfuric acid, alkylsulfonic acids, and arylsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, l-propanesulfonic acid, 2-propanesulfonic acid, benzenesulfonic acid, p-chlorobenzenesulfonic acid, p-nitrobenzenesulfonic acid, p-toluenesulfonic acid, l,Z-naphthaIene-disulfonic acid, m-benzenedisulfonic acid, and the like.
  • the preferred catalyst is sulfuric acid.
  • Other inorganic acids, such as phosphoric and phosphorous acids can be used but they are considerably less effective.
  • the phosphite starting materials which can be used are those containing cyclic structures such as the spirocyclic and bicyclic phosphites. Usually such phosphites are based on polyols which contain 2-8 hydroxyl groups in the 1,2- or 1,3-positions in their structure. Examples of such compositions are diols, such as ethylene glycol, 1,2- and 1,3-propanediol, and 2,2-dimethyl- 1,3-propanediol; triols, such as glycerol and trimethylol propane; tetrols, such as pentaerythritol; and hexols, such as dipentaerythritol, and the like.
  • diols such as ethylene glycol, 1,2- and 1,3-propanediol, and 2,2-dimethyl- 1,3-propanediol
  • triols such as glycerol and trimethylol propane
  • phosphites which can be used are those having the following structural formulae:
  • R c o P-OR 2 R c o l CH-O C P-OR R III CH O 5 R C P IV /o cH 2 /c H -O ⁇ RO-P C O--CH CH -O
  • R, R R and R maybe the same or different and may be hydrogen.
  • R may be an alkyl radical or a haloalkyl radical having from 1 to 6 carbon atoms and mixtures thereof;
  • R may be an alkyl, or hydroxyalkyl, or hyr droxyalkyl radical having from 1 to 4 carbon atoms and mixtures thereof;
  • R may be an alkyl or haloalkyl radical having from 1 to carbon atoms, an aryl or haloaryl radical having from 6 to 10 carbon atoms, or an aralkyl or alkyaryl group having from 7 to' 12 carbon atoms wherein the aralkyl and alkaryl radicals can contain halogen substituents, or mixtures thereof.
  • R may also be an alkylene radical having from 2 to 6 carbon atoms linking two cyclic phosphites having the structural formulae I, II or IV above, the two cyclic structures being the same or different.
  • R is 2-chloroethyl and optimumly where R is lchloro-2-propyl.
  • the resultant phosphonates contain hydroxyl groups.
  • the products contain hydroxymethyl groups.
  • the novel compositions of the invention are obtained by heating the phosphite and the catalyst to about 50130C. preferably 80l00C., usually in an appropriate solvent. If the phosphite is a liquid, the solvent may be omitted.) Methanol is then added dropwise at this temperature range. The resulting mixture is then maintained within the temperature range of 50l30C., and heating is continued until all of the phosphite has been consumed.
  • the time to complete the reaction will vary depending on the type of phosphite and the amount of methanol and catalyst employed. For example, the reaction time may be as short as one hour or as long as 6 hours.
  • IR infrared
  • the amount of methanol used may vary from about 2 to about 5 moles per phosphite equivalent, preferably about 2.5 moles of methanol per phosphite equivalent. An excess of greater than about 5 moles of methanol per phosphite equivalent should be avoided as such an excess may result in the formation of undesirable side products.
  • the amount of acid catalyst used may vary from about 0.1 to about 10 mole percent per mole of phosphite. Normally, the preferred amount of acid catalyst varies between one and two mole percent.
  • any inert organic solvent can be employed in the process of this invention such as, hexane, tetrahydrofuran, benzene, toluene, xylene, chloroform, carbon tetrachloride, dichloroethane, and the like.
  • the preferred solvent is dichloroethane.
  • the weakly acidic solution about pI-I4-pI-l6, is neutralized with base, such as sodium methoxide or gaseous ammonia.
  • base such as sodium methoxide or gaseous ammonia.
  • the solution is filtered, if necessary, and then concentrated, preferably under reduced pressure. at about l0Ol50C. to remove solvent, if any, methanol and volatile byproducts.
  • the product is recovered as a pot residue.
  • An alternate process involves dissolving the phosphite in methanol, adding the catalyst, and refluxing the resulting solution until all of the phosphite has been consumed. This is a less preferred method since the reaction is initially exothermic and may become diffcult to control, especially in a large scale run.
  • compositions are useful as flame retardants in organic resins such as polyvinyl chloride (PVC), polyesters, polysulfones, polycarbonates, polyamides and polyurethanes.
  • PVC polyvinyl chloride
  • polyesters polysulfones
  • polycarbonates polycarbonates
  • polyamides polyurethanes
  • the phosphonates of the invention contain hydroxyl groups and are, therefore, especially useful in polyurethane production when employed with conventional polyols as co-reactants with polyisocyanates.
  • compositions of the invention are very fluid oils at room temperature and have good solubility in the polyols normally used in the production of polyurethane foams. Since the compositions of the invention contain hydroxyl groups capable of reacting with the polyisocyanates normally employed in polyurethane production, permanent flame protection is achieved as the compositions are chemically bound to the polymer backbone. In addition, the unusually high phosphorus content of these compositions renders them extremely effective as flame retardants even when used at relatively low concentrations of about 10% or less by weight in a polyurethane foam, although concentrations as high as about 30% by weight may also be employed.
  • reaction solution was neutralized with a small volume of ammonia gas, filtered to remove small amounts of precipitate, and then concentrated under reduced pressure (-15 mm. Hg.) at about 100C. pot temperature to remove solvent and volatile by-products.
  • the product was recovered as a pot residue and was a colorless fluid oil.
  • the phosphite was prepared in situ by a transesterification of pentaerythritol with trimethyl phosphite and I the dimethyl phosphite was used as catalyst.
  • the resulting phosphite was 3,9-dimethoxy-2,4,8,1,0-tetraoxa- 3 ,9-diphosphaspiro[ 5 .5 undecane.
  • This phosphite was prepared according to the method described in Example 1 of US. Pat. No. 2,841,608 to Hechenbleikner et al.
  • the phosphonate was prepared as follows:
  • Example 15 of these patents is carried out using triphenyl phosphite, an alkyl alcohol, i.e., butanol, and pentaerythritol which are transesterified and then thermally rearranged without using a catalyst at a temperature of 150l70C. to form a mixture of phosphonates.
  • Example 15 of the prior art patents was modified by replacing butanol with methanol and the molar ratios of triphenyl phosphite to pentaerythritol were changed from 1:1 to 2:1 to correspond with the ratios of similar materials used in this invention.
  • triphenyl phosphite 155 g., 0.5 mole
  • methanol 32 g., 1.0 mole
  • NaH- catalyst 0.3 g.
  • the water condenser was then replaced by a tall air condenser topped by a short water condenser and the reaction solution heated to 160170C. and held at this temperature for about 10l5 hours. Phenol and volatile by-products were then distilled under reduced pressure, giving the product as a viscous, tan oil.
  • the No. of this product is lower than any of the phosphonat'es of the invention.
  • GPC Gel Permeation Chromatography
  • Standard samples are generally chromatographed with the samples being tested so that the molecular weight of the samples can be determined relative to the molecular weight of the standards.
  • the samples are detected by monitoring-the change of refractive index (ARI) of the effluent from the end of the column. If the sample had a refractive index (RI) different from that of the mobil phase, the difference is detected and output to a strip chart recorded.
  • the difference may be either positive or negative with respect to the back- I ground R1 of the solvent.
  • Example 15 of the prior art patents and the composition of Example 11 of this invention each indicated the presence of at least two main types of components.
  • the components comprising the Example 15 composition had refractive indices greater than the standards whereas those of the Example 11 compositions had refractive indices less than the standards, thereby establishing that while these compositions ostensibly appear to be similar, they are actually two different types' o f phosphonates.
  • the Example 15 composition did not contain .hydrogen phosphonate moieties whi ch are present in substantial amounts (30-50%) in all of the pho'sphonates of the invention.
  • EXAMPLE vn This example illustrates the utility of the compositions of the invention as flame retardants in rigid urethane foam.
  • Polyol A was a propoxylated N-aminoethylpiperazine, OH No. 520
  • Polyol B was a propoxylated sorbitol, OI-I No. 490.
  • the rigid urethane foam was prepared by'a handmix technique using a conventional one-shot process.
  • the foam obtained was tested using the oxygen index method of ASTM D-2863, giving an oxygen index (O.I.) of 24.7.
  • the untreated foam i.e., a control made without the composition of Example I, gave an 0.1. of 20.6.
  • a substantial improvement in the flameresistant properties of a rigid urethane foam was achieved using compositions of the invention.
  • Example I Composition of Example I 24.7 Composition of Example 11 25.0 Phosphorous type flame retardant-I;
  • compositions of the invention are superior to the commercial phosphorus-type flame retardants.
  • a mixture of hydrogenphosphonates and methylphosphonates obtained by reacting a cyclic phosphite selected from the group having the structure I I H R c O ⁇ P-OR 2 R -C-O wherein R and R may be the same or different and are hydrogen, alkyl or haloalkyl having from 1 to 6 carbon atoms, and R is alkyl or haloalkylhaving from 1 to 10 carbon atoms, aryl or haloaryl having from 6 to 10 carbon atoms, alkaryl or aralkyl having from 7 to 12 carbon atoms wherein the alkaryl and aralkyl groups can also contain halogen substituents, or alkylene having from 2 to 6 carbon atoms linking two cyclic phosphites of said structure I;
  • R is alkyl or hydroxyalkyl having from 1 to 4 carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Fireproofing Substances (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
US535749A 1974-02-07 1974-12-23 Compositions comprising mixtures of hydrogenphosphonates and methylphosphonates Expired - Lifetime US3927146A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US535749A US3927146A (en) 1974-02-07 1974-12-23 Compositions comprising mixtures of hydrogenphosphonates and methylphosphonates
GB3001/75A GB1503561A (en) 1974-02-07 1975-01-23 Mixtures of hydrogenphosphonates and methylphosphonates and method of making the same
IT67287/75A IT1032571B (it) 1974-02-07 1975-02-04 Composizione di fosfonati particolarmente utile come ritardatore di fiamma per materie plastiche e procedimento per la sua preparazione
FR7503597A FR2260600B1 (enrdf_load_html_response) 1974-02-07 1975-02-05
DE19752504828 DE2504828A1 (de) 1974-02-07 1975-02-05 Massen aus mischungen von hydrogenphosphonaten und methylphosphonaten sowie verfahren zu ihrer herstellung
JP50015838A JPS50108224A (enrdf_load_html_response) 1974-02-07 1975-02-06

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US44041174A 1974-02-07 1974-02-07
US535749A US3927146A (en) 1974-02-07 1974-12-23 Compositions comprising mixtures of hydrogenphosphonates and methylphosphonates

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JP (1) JPS50108224A (enrdf_load_html_response)
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FR (1) FR2260600B1 (enrdf_load_html_response)
GB (1) GB1503561A (enrdf_load_html_response)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071583A (en) * 1975-04-07 1978-01-31 Borg-Warner Corporation Cyclic phosphonates
US4082897A (en) * 1976-06-10 1978-04-04 Borg-Warner Corporation Glass lamination utilizing cyclic phosphonates

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3515776A (en) * 1964-02-28 1970-06-02 Hooker Chemical Corp Mixed esters of phosphonic acid and preparation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3515776A (en) * 1964-02-28 1970-06-02 Hooker Chemical Corp Mixed esters of phosphonic acid and preparation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071583A (en) * 1975-04-07 1978-01-31 Borg-Warner Corporation Cyclic phosphonates
US4082897A (en) * 1976-06-10 1978-04-04 Borg-Warner Corporation Glass lamination utilizing cyclic phosphonates

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GB1503561A (en) 1978-03-15
FR2260600A1 (enrdf_load_html_response) 1975-09-05
JPS50108224A (enrdf_load_html_response) 1975-08-26
FR2260600B1 (enrdf_load_html_response) 1978-10-06
IT1032571B (it) 1979-06-20
DE2504828A1 (de) 1975-08-14

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Owner name: UNIROYAL CHEMICAL COMPANY, INC., WORLD HEADQUARTER

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UNIROYAL, INC., A NEW YORK CORP.;REEL/FRAME:004488/0204

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Effective date: 19870130